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In this study, the induction plasma spheroidization (IPS) technique was adopted to improve the microstructure and properties of the traditional agglomerated ZrO2-7wt%Y2O3 (YSZ) powders used in thermal barrier coating (TBC) applications. Compared with agglomerated YSZ powders, IPS-treated powder has a more desirable microstructure, and the overall performance of the spray powders for TBC preparation is significantly improved. Specifically, IPS-treated powder has a dense, solid, defect-free, and chemically uniform microstructure, and its apparent density, flowability, and powder strength are significantly improved, which is believed to substantially enhance the coating performance when prepared with this IPS-treated powder.
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Contemporary gas turbine engines rely on thermal barrier coatings (TBCs), which protect the structural components of the engine against degradation at extremely high operating temperatures (1300-1500 °C). The operational efficiencies of aircraft engines have seen significant improvement in recent years, primarily through the increase in operating temperatures; however, the longevity of TBCs can be potentially impacted by several types of degradation mechanisms. In this comprehensive study, a wide range of novel columnar suspension plasma sprayed (SPS) coatings were developed for their erosion, calcium-magnesium-aluminum-silicate (CMAS), and furnace cycling test (FCT) performance. Through a comprehensive investigation, the first of its kind, we achieved a range of SPS microstructures by modifying the spray parameters and measuring their microhardness, fracture toughness, column densities, and residual stresses using Raman spectroscopy. We were able to produce dendritic, lateral, branched, and columnar microstructures with a unique set of processing parameters. Coatings enhanced with a refined columnar microstructure, achieved by modulating the distance from the plasma torch, exhibited superior thermal cycling resilience. Conversely, the development of a columnar microstructure with dendritic branches, obtained by decreasing the robot's traversal speed during deposition, bolstered resistance to erosion and minimized damage from molten CMAS infiltration, thereby notably augmenting the coating's lifespan and robustness. The pursuit of the optimal columnar microstructure led to the conclusion that for each SPS coating, a general framework of optimization needs to be conducted to achieve their desired thermo-chemico-mechanical resistance as the properties required for TBCs are intertwined.
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This paper focused on studying the performance of a nanostructured thermal barrier coating (TBC) system deposited by APS, which had a bond coat with inter-lamellar porosities that resulted during the manufacturing process. The higher porosity level of the bond coat was studied as a possible way to keep the thickness of the TGO under control, as it is distributed on a higher surface, thereby reducing the chance of top-coat (TC) spallation during long-term oxidation and high-temperature thermal shock. The TBC system consisted of nanostructured yttria partially stabilized zirconia (YSZ) as a top coat and a conventional NiCrAlY bond coat. Inter-lamellar porosities ensured the development of a TGO distributed on a higher surface without affecting the overall coating performance. Based on long-term isothermal oxidation tests performed at 1150 °C, the inter-lamellar pores do not affect the high resistance of nanostructured TBCs in case of long-term iso-thermal oxidation at 1150 °C. The ceramic layer withstands the high-temperature exposure for 800 h of maintaining without showing major exfoliation. Fine cracks were discovered in the ceramic coating after 400 h of isothermal oxidation, and larger cracks were found after 800 h of exposure. An increase in both ceramic and bond-coat compaction was observed after prolonged high-temperature exposure, and this was sustained by the higher adhesion strength. Moreover, in extreme conditions, under high-temperature thermal shock cycles, the TBC withstands for 1242 cycles at 1200 °C and 555 cycles at 1250 °C.
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Thermal spray coatings are material systems with unique structures and properties that have enabled the growth and evolution of key modern technologies (i.e., gas turbines, structurally integrated components, etc.). The inherent nature of these sprayed coatings, such as their distinctive thermal and mechanical properties, has been a driving force for maintaining industrial interest. Despite these benefits and proven success in several fields, the adoption of thermal spray technology in new applications (i.e., clean energy conversion, semiconductor thermally sprayed materials, biomedical applications, etc.) at times, however, has been hindered. One possible cause could be the difficulty in concurrently maintaining coating design considerations while overcoming the complexities of the coatings and their fabrication. For instance, a coating designer must consider inherent property anisotropy, in-flight decomposition of molten material (i.e., loss of stoichiometry), and occasionally the formation of amorphous materials during deposition. It is surmisable for these challenges to increase the risk of adoption of thermal spray technology in new fields. Nevertheless, industries other than those already mentioned have benefited from taking on the risk of implementing thermal spray coatings in their infrastructure. Benefits can be quantified, for example, based on reduced manufacturing cost or enhanced component performance. In this overview paper, a historical presentation of the technological development of thermal spray coatings in several of these industries is presented. Additionally, emerging industries that have not yet attained this level of thermal spray maturation will also be discussed. Finally, where applicable, the utility and benefits of multilayer functional thermal spray coating designs will be demonstrated.
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Countless research has suggested Yttria-stabilized Zirconia (YSZ) to be a top candidate for being implemented as thermal barrier coatings (TBC). However, when exposed to prolonged service, temperature and stress variations succeed in initiating a catastrophic phase transformation from tetragonal to monoclinic structure in Zirconia. Hence, the estimation of endurance for YSZ-based TBC is necessary to minimize failure in such situations. The main purpose of this research was to determine the relationship between tribological investigations and the estimated lifespan of YSZ coatings accurately. The study used various methods such as wear resistance testing, optical profilometry, specific wear rate, and coefficient of friction to estimate the maximum durability of TBCs. The research also provided insights into the composition and microstructure of the TBC system and found the optimized concentration of Yttrium doping to be 3.5 wt %. The study discovered that erosion was the main cause of roughness depreciation from SN to S1000. The estimation of the service life was primarily made based on optical profilometry, specific wear rate (SWR), coefficient of friction (COF) and wear resistance values which were further supported by the results of chemical characterization of the samples through electron dispersive spectroscopy (EDS), wavelength dispersive spectroscopy (WDS) and X-Ray Diffraction (XRD) analysis. The results were reliable and accurate and suggested future areas of investigation, such as 3D profilometry for surface roughness and thermal conductivity evaluation using laser-assisted infrared thermometers.
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As the operation temperature of next generation gas turbine is targeted to be 1800 °C toward a higher efficiency and lower carbon emission, the near-infrared (NIR) thermal radiation becomes a major concern for the durability of the metallic turbine blades. Although thermal barrier coatings (TBCs) are applied to provide thermal insulations, they are translucent to the NIR radiation. It is a major challenge for TBCs to achieve optically thick with limited physical thickness (usually < 1 mm) for effectively shielding the NIR radiation damage. Here, an NIR metamaterial is reported, where a Gd2 Zr2 O7 ceramic matrix is randomly dispersed with microscale Pt (0.53 vol%) nanoparticles with a size of 100-500 nm. Attenuated by the Gd2 Zr2 O7 matrix, a broadband NIR extinction is achieved through the red-shifted plasmon resonance frequencies and higher-order multipole resonances of the Pt nanoparticles. A very high absorption coefficient of ≈3 × 104 m-1 , approaching the Rosseland diffusion limit for a typical coating thickness, minimizes the radiative thermal conductivity to ≈10-2 W m-1 K-1 and successfully shields the radiative heat transfer. This work suggests that constructing a conductor/ceramic metamaterial with tunable plasmonics could be a strategy to shield NIR thermal radiation for high temperature applications.
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The growth stress induced by thermally grown oxide (TGO) is one of the main reasons for the failure of thermal barrier coatings (TBCs). In this study, the failure behavior of TBCs was examined based on different growth modes of TGO. A TBC thermo-mechanical model with a simplified sinusoidal interface morphology was established by the secondary development of a numerical simulation. The plasticity and creep behavior of materials were considered. Based on the subroutine development, the non-uniform growth of the TGO layer was realized. Cohesive elements were also applied to the TC/TGO interface. The stress distribution and evolution at the TC/TGO interface were investigated. Then, the cracking behavior near the interface was studied. The results show that lateral growth causes the off-valley site to replace the previous off-peak site as a vulnerable site. The non-uniform growth accelerates damage in the off-valley site, which leads to a change in the failure behavior. These results will provide significant guidance for understanding the TBC failure and the development of advanced TBCs.
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The failure of thermal barrier coatings (TBCs) during operation depends mainly on the thermal mismatch between the ceramic top coat (TC) and the metal bond coat (BC). The thermal mismatch at the interface is influenced by the dynamic changes in the composition and morphology of the thermally grown oxide (TGO) between TC and BC during thermal cycling. This work focuses on the establishment of a TGO dynamic growth model, which considers the changes in TGO composition and morphology for investigating the effect of dynamic growth of TGO on local mismatch stresses during thermal cycling. The results show that the sharp locations at the TGO/BC interface are more prone to high tensile stresses during thermal cycling due to the uneven growth behavior of TGO, leading to crack initiation. The valley region of the interface is in a state of compressive stress σxx during the early stages of thermal exposure. The peak region preferentially forms a concentration of tensile stress σyy. Once large-scale "layer" (Ni, Co)Al2O4-based spinel-like mixed oxides(MO) growth occurs in TGO, the stress σxx changes from compressive stress to tensile stress in the valley region, eventually forming high tensile stress (Max: +158 MPa). The maximum tensile stress σyy in the peak region is increased to 256 MPa, which is more than two times larger than the early period of thermal exposure. As a result, the dramatic changes in local stresses seriously affect the time and location of microcracks.
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Thermal barrier coatings (TBCs) are widely used to protect high-temperature components against harsh environments, such as extremely high temperatures. In this work, a second generation Ni-based single crystal superalloy (DD6) was treated in two ways: (1) via simple surface sandblasting under different pressures with no additional coating, and (2) through simple surface sandblasting under different pressures and then by applying NiCoCrAlYHf (HY5) coatings. The effects of pre-treatment (sandblasting) and the HY5 coating on the surface recrystallization of the alloy were thoroughly investigated. According to the results, both sandblasting pressure and the presence or absence of a coating significantly influence surface recrystallization. In particular, the critical sandblasting pressure for recrystallization increased the maximum recrystallization depth in both the coated and uncoated samples. Meanwhile, the recrystallization depth of the alloy with a coating was reduced compared to that without a coating. In addition, the number of recrystallized cells in the coated alloy was decreased, which indicated that the HY5 coating effectively reduced the degree of recrystallization.
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Interfacial stress-strain fields become complicated in thermal barrier coatings (TBCs) under cyclic thermal loading, which affects the stability and spalling failure of TBCs directly. The convex and concave interfacial structures of TBCs were approximated as a multilayer cylinder model, and an analytical method of TBCs for shakedown analysis was established. A series of 8-YSZ TBC specimens were prepared by the plasma spraying process, followed by isothermal and thermal shock tests. The results showed that the stability limit is significantly greater than the elastic limit, the limit for the convex model was higher than that in the concave model, the first failure occurs in the concave area, and the main failure mode of a thermal barrier coating is the appearance of cracks at the interface layer during a thermal shock test. For the coating samples prepared in this study, the stability limits were between 950 °C and 1050 °C, and the validity of the stability limit analysis model of a multilayer structure was verified.
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High entropy alloys (HEAs) are multi-elemental alloy systems that exhibit a combination of exceptional mechanical and physical properties, and nowadays are validating their potential in the form of thermal sprayed coatings. In the present study, a novel synthesis method is presented to form high entropy alloy coatings. For this purpose, thermal sprayed coatings were deposited on Stainless Steel 316L substrates using atmospheric plasma spraying technique with subsequent annealing, at 1000 °C for 4 h, to assist alloy formation by thermal diffusion. The coatings in as-coated samples as well as in annealed forms were extensively studied by SEM for microstructure and cross-sectional analysis. Phase identification was performed by X-ray diffraction studies. The annealed coatings revealed a mixed BCC and FCC based HEA structure. Potentiodynamic corrosion behavior of SS316L sprayed as well as annealed coatings were also carried out in 3.5% NaCl solution and it was found that the HEA-based annealed coatings displayed the best corrosion resistance 0.83 (mpy), as compared to coated/non-annealed and SS 316 L that showed corrosion resistance of 7.60 (mpy) and 3.04 (mpy), respectively.
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The market needs for increased engine efficiency and environmentally friendly solutions remain the key drivers for the aerospace industry. These efficiency gains will be achieved by meeting the challenges of higher engine operating temperatures, weight reduction, and novel surface solutions for increased component longevity. A critical question to address is if the thermal spray (TS) industry can continue to meet the challenges and demands seen by the airlines and the engine manufacturers. In addition to non-aerospace influences, the COVID-19 pandemic has dramatically affected the landscape of industry growth, not only directly on airlines but also on the associated supply chain. This article reviews this market, its suppliers, and identifies the challenges and opportunities for future growth. Primary focus is on technology and what will be required to bring about reliable, robust, and cost-effective TS solutions into the marketplace. Several issues affecting the global landscape of the aerospace industry are discussed including (1) sustainability, (2) technology, (3) cost of ownership, (4) evolving marketplace, (5) workforce and behavior, and (6) supply chain vitality. An important question to address is if the TS industry can accelerate development with its supply chain and have the ability to commercialize technology more efficiently. Despite the market setbacks from the pandemic and previous issues with the Boeing 737 MAX fleet, the aerospace industry is poised to make significant advancements. These will create new opportunities for thermal spray technology in materials, equipment, and processes. To deliver on them, the implementation of Industry 4.0 along with the investment in human resources is more critical than ever. Based on the findings, the authors project a bright long-term future for both the aerospace and thermal spray industries.
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MCrAlX powder compositions (M = Ni,Co and X = Y, Hf, Si or combination) are often thermally sprayed via vacuum plasma spray (VPS), low pressure plasma spray (LPPS) or high velocity oxy-fuel to produce high temperature oxidation and hot corrosion resistant bond coats for thermal barrier coatings (TBCs). Cold spray technology is currently considered as a promising alternative to the traditional thermal spray solutions, having the advantage of delivering oxide-free and very dense metallic coatings at relatively lower costs compared to VPS and LPPS. NiCoCrAlY and NiCoCrAlYHfSi bond coats were deposited using a high pressure cold spray system and the influence of feedstock properties on the deposited bond coats were investigated. To improve NiCoCrAlYHfSi bond coat deposition, laser assisted cold spray (LACS) was employed. The results show that LACS can be successfully used to deposit this particular powder while eliminating nozzle erosion and low deposition efficiency disadvantages observed with conventional cold spray. To identify the optimal LACS setup for deposition of dense and uniform coatings, different laser/spray jet configurations were examined. TBCs with bond coats sprayed at the optimal configuration were assessed isothermally at 1150 °C in air for up to 500 h, and the results showed formation of a thermally grown oxide layer composed of predominantly Al2O3 with embedded small clusters of Hf-Y-rich oxides.
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This study deals with the numerical analysis of the plasma jet behavior close to the substrate surface depending on its topography. It uses a 2D axisymmetric time-dependent CFD model solved with the Ansys Fluent 2020/R1 package. The model takes into consideration the nonlinear thermophysical properties and turbulent phenomena of the plasma jet as well as its interaction with the microtextured substrate. Representative substrate topographies were considered as a boundary condition in the numerical simulations. They correspond to the bond coats used in Thermal Barrier Coating technology, actually APS sprayed NiCrAlY coatings which were experimentally microtextured using various laser unit operational conditions resulting in different substrate topographies. The numerical calculations showed that the substrate topography, modified and controlled in this work by microtexturing, disturbs the homogeneity of the pressure field in the substrate boundary layer resulting in the periodical pressure fluctuation. It was also observed that the relative local pressure disturbance is more significant in the substrate outer regions than close to the centerline. Then, based on the results of numerical calculations, the potential movement of feedstock particles near to the substrate was discussed. It was concluded that the deposition of fine powders, characterized by a low Stokes number, will be influenced by the pressure field distribution near to the substrate and will take place mainly in the local high-pressure zones. Furthermore, the local swirl of plasma taking place in each fine microtexture, created here by laser ablation, privileges the deposition of such particles on the surface asperities. These observations show that the CFD code modeling opens the possibility of predicting the movement and deposition of particles during plasma spraying, which is essential for understanding coating deposition mechanisms in suspension plasma spray.
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This paper shows the results of an investigation on the synthesis of non-porous and nanocrystalline ZrO2-Gd2O3 layers by metalorganic chemical vapor deposition (MOCVD) with the use of Zr(tmhd)4 (tetrakis(2,2,6,6-tetramethyl-3,5-heptanedionato)zirconium(IV)) and Gd(tmhd)3 (tris(2,2,6,6-tetramethyl-3,5-heptanedionato)gadolinium(III)). Argon and air were used as carrier gases. The molar content of Gd(tmhd)3 in the gas reaction mixture was as follows: 10% and 20%. The layers were synthesized on tubular substrates made of quartz glass at the temperatures of 550-700 °C. Synthesis conditions were established using the Grx/Rex2 expression (Gr is the Grashof number; Re is the Reynolds number; x is the distance from the gas inflow point). The value of this criterion was below 0.01. ZrO2-Gd2O3 layers synthesized at 600-700 °C were crystalline. When the molar content of Gd(tmhd)3 in the gas reaction mixture was 10 mol.%, a relationship between the chemical composition of the gas reaction mixture and that of the deposited layer could be observed. The synthesized layers underwent scanning electron microscopy, as well as X-ray analysis. The transparency of coated and uncoated glass was tested using UV-Vis spectroscopy. Their chemical composition was examined with the use of an EDS analyzer.
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Yttria stabilized zirconia (YSZ) thermal barrier coatings (TBCs) deposited on CoNiCrAlY oxidation protective bond coats are commonly required in temperature regimes up to 1200 °C (e.g., hot gas turbine regions) due to their superior thermal behavior and mechanical properties. For temperatures up to around 900 °C, oxidation protection can be alternatively provided by metallic-ceramic Cr-CrxOy coatings. For the present research, Cr-CrxOy atmospheric plasma sprayed (APS) and YSZ-CoNiCrAlY APS-high velocity oxy-fuel TBC coatings were deposited on a NiCr20Co18Ti substrate. The samples were isothermally heat treated at 900 °C for 10 h in an environmental atmosphere and subsequently isothermally oxidized at the same temperature for 1200 h. Investigations of the physical, chemical, and mechanical properties were performed on the as-sprayed, heat-treated, and oxidized samples. The oxidation behavior, microhardness, cohesion, and adhesion of the samples were correlated with the microstructural investigations and compared to the conventional TBC system. It could be shown that heat treating decreased the Cr-CrxOy coatings crack susceptibility and led to the formation of a protective thermally grown Cr oxide layer. The experimental work on the YSZ-CoNiCrAlY system revealed that the phase composition of the bond coat has a direct influence on the oxidation protection of the coating system.
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The increased demand for high performance gas turbine engines has resulted in a continuous search for new base materials and coatings. With the significant developments in nickel-based superalloys, the quest for developments related to thermal barrier coating (TBC) systems is increasing rapidly and is considered a key area of research. Of key importance are the processing routes that can provide the required coating properties when applied on engine components with complex shapes, such as turbine vanes, blades, etc. Despite significant research and development in the coating systems, the scope of electrodeposition as a potential alternative to the conventional methods of producing bond coats has only been realised to a limited extent. Additionally, their effectiveness in prolonging the alloys' lifetime is not well understood. This review summarises the work on electrodeposition as a coating development method for application in high temperature alloys for gas turbine engines and discusses the progress in the coatings that combine electrodeposition and other processes to achieve desired bond coats. The overall aim of this review is to emphasise the role of electrodeposition as a potential cost-effective alternative to produce bond coats. Besides, the developments in the electrodeposition of aluminium from ionic liquids for potential applications in gas turbines and the nuclear sector, as well as cost considerations and future challenges, are reviewed with the crucial raw materials' current and future savings scenarios in mind.
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Time-domain spectroscopy (TDS) in the terahertz (THz) frequency range is gaining in importance in nondestructive testing of dielectric materials. One application is the layer thickness measurement of a coating layer. To determine the thickness from the measurement data, the refractive index of the coating layer must be known in the surveyed frequency range. For perpendicular incidence of the radiation, methods exist to extract the refractive index from the measurement data themselves without prior knowledge. This paper extends these methods for non-perpendicular incidence, where the polarization of the radiation becomes important. Furthermore, modifications considering effects of surface roughness of the coating are introduced. The new methods are verified using measurement data of a sample of Inconel steel coated with yttria-stabilized zirconia (YSZ) and with COMSOL simulations of the measurement setup. To validate the thickness measurements, scanning electron microscopy (SEM) images of the layer structure are used. The results show good agreement with an average error of 1% for the simulation data and under 4% for the experimental data compared to reference measurements.
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Several applications, where extreme conditions occur, require the use of alloys often containing many critical elements. Due to the ever increasing prices of critical raw materials (CRMs) linked to their high supply risk, and because of their fundamental and large utilization in high tech products and applications, it is extremely important to find viable solutions to save CRMs usage. Apart from increasing processes' efficiency, substitution, and recycling, one of the alternatives to preserve an alloy and increase its operating lifetime, thus saving the CRMs needed for its manufacturing, is to protect it by a suitable coating or a surface treatment. This review presents the most recent trends in coatings for application in high temperature alloys for aerospace engines. CRMs' current and future saving scenarios in the alloys and coatings for the aerospace engine are also discussed. The overarching aim of this paper is to raise awareness on the CRMs issue related to the alloys and coating for aerospace, suggesting some mitigation measures without having the ambition nor to give a complete overview of the topic nor a turnkey solution.
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In an effort to protect metal substrates from extreme heat, polymer-clay multilayer thin films are studied as expendable thermal barrier coatings. Nanocomposite films with a thickness ranging from 2 to 35 µm were deposited on steel plates and exposed to the flame from a butane torch. The 35 µm coating, composed of 14 deposited bilayers of tris(hydroxymethyl)aminomethane (THAM)-buffered polyethylenimine (PEI) and vermiculite clay (VMT), decreased the maximum temperature observed on the back side of a 0.32 cm thick steel plate by over 100 °C when heated with a butane torch. Upon exposure to high temperature, the polymer and amine salt undergo pyrolysis and intumesce, subsequently forming a char and blowing gas. The char encases the nanoclay platelets, and a ceramic bubble is formed. The macro-scale bubble, in tandem with the nanocomposite coating properties, increases resistance to heat transfer into the underlying metal substrate. This heat shielding behavior occurs through radiative effects and low aggregate through-plane conductivity resulting from multilayer nanodomains and intumesced porosity (i.e., conduction through the gas as the film expands to form a ceramic bubble). These relatively thin and lightweight films could be used to protect important metal parts (in automobiles, aircraft, etc.) from fire-related damage or other types of transient high-temperature situations.